CN1027176C - Hydrocracking process with polycyclic aromatic dimer removal - Google Patents
Hydrocracking process with polycyclic aromatic dimer removal Download PDFInfo
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- CN1027176C CN1027176C CN91108862A CN91108862A CN1027176C CN 1027176 C CN1027176 C CN 1027176C CN 91108862 A CN91108862 A CN 91108862A CN 91108862 A CN91108862 A CN 91108862A CN 1027176 C CN1027176 C CN 1027176C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
Abstract
A process for separation and removal of stable polycyclic aromatic dimer foulants from refinery process streams by blending a paraffinic stream with a portion of heavy effluent from a hydrocracking reactor to induce precipitation of foulant, which may then be separated and removed from the hydrocracker. Additional embodiments include introduction of flocculating agents and adjusting the temperature of the blend.
Description
The present invention relates to from refining of petroleum oil stream, remove the compound of decontaminate processing units, particularly about the method for the polycyclc aromatic compound of separating stable, these compounds form in the hydrocracking process, and form fouling and choked flow is damaged dirty processing units around the neutralization of dirty processing units.
The refining of petroleum hydrocracking process is well-known, and in continuous development, this technology has improved the grade of hydrocarbon mixture, and more valuable petroleum products can be provided.
Hydrocracking is a very strict hydrotreatment operation, and wherein the high-molecular weight compound is cracked into low-boiling point material.Compare with hydrotreatment, owing to hydrocracking carries out under comparatively high temps, and the reaction times is longer, so increased difficulty.The hydrogen pressure that increases can be controlled settling and fouling of catalyst.Different with heat or cracking catalyst, hydrocracking can reduce the molecular weight of aromatic compound, and can satisfy the big special requirement of treated oil stream of recycle stock, coke chemicals or the coal tar of autocatalysis of aromatoising substance Tathagata or thermo-cracking.For example, the catalysis recycle stock can be cracked into naphtha fraction, and it is the good raw material that high octane gasoline or petroleum chemistry aromatoising substance are produced in catalysis.
Hydrocracking is widely used in and distillates stock oil, and its technology can be used to refining stock oil to obtain the low high quality kerosene of sulfur-bearing and nitrogen, diesel oil or jet fuel oil.The light-end products that hydrocracking produces also is rich in Trimethylmethane, and it is a kind of important raw material for alkylation.
Consider the needs of restitution oil condition and processing synthetic crude, hydrocracking is extremely important.So the hydrocracking hydrogen richness is that 10～11% Residual oil, Tar sands and shale oil are more more desirable than the grade that improves the coal tar that only contains 6% hydrogen and high-content fragrance ingredient.
At present, because worldwide the source of making refining raw material with lightweight, sweet crude oil more and more lacks, so the trend that higher-boiling compound is changed into low-boiling compound is just arranged greatly.This " oil foot " or " difficult processing " part as polycyclc aromatic compound, and has been aggravated the dirty scale problems of potential owing to can produce the ring compound that a large amount of heavys transform at initial refining stage.Increase hydrocarbon hydrocracking reaction device and the such processing unit (plant) of Residual oil desulfurizer, make that must economically to solve scale problems more urgent.
Along with the increase to the distillate fuel demand, refinery has been installed the hydrocracking device vacuum gas oil (VGO) has been transformed into jet fuel and diesel oil.And develop several catalyzer, these catalyst towards heavy raw material oil have good cut selectivity, high activity of conversion and stability.
In recent years, the development trend of high yield reactor is to adopt the catalyzer than the long life with a large amount of molecular sieves, the well-known catalyzer that one class has the height molecular sieve is " zeolite " type catalyzer, the result that zeolite catalyst acts in the hydrocarbon hydrocracking reaction device forms aromatics, has so just increased again to have the existence that forms the compound of stablizing polycyclc aromatic compound.In addition, these stable polycyclc aromatic compounds help fouling of catalyst and close-burning.When the hydrocarbon hydrocracking reaction actuator temperature reached 850～900 °F, discovery had increased the formation of stable Ppolynuclear aromatic dimeric compounds in for some time under being in before catalyst changeout more " reaction (operation) end " condition.Therefore, as reducing refining processing units fouling and the coked method of catalyzer, press for effective, economic removing and stablize improving one's methods of polycyclc aromatic compound.
Except a large amount of conversion overhead products, another development trend of the eighties is that oil at the bottom of the unconverted separation column is sent into the device that resembles FCC, cracking of ethylene and so on by the hydrocracking device, it can also be sent into lubricating oil source mill as the high quality paraffin raw material and therefrom makes a profit.The oil foot that belongs to the VGO-scope its in the hydrocracking device, be desulfurized between residence time, denitration and highly saturated.
The U.S.3 of on November 9th, 1971 bulletin, 619, people such as 407(Hendricks) introduce a kind of hydrocracking catalyst that is used for using hydrocracking, but also related to the problem of some aspect that the present patent application emphasized.This patent documentation has disclosed the formation problem of polycyclc aromatic compound, said compound serves as with reference to determining with the benzo coronene, and it has described this compounds " deposition " known tendency on flow device such as the heat-exchanger surface under the water cooler.Claimed technical solution described in this patent documentation is to remove or " separation " hydrocracking effluent part, is present in the concentration of Ppolynuclear aromatic material in this effluent with minimizing.
Licensed to people's such as Lamb US4 on May 8th, 1984,447,315 have disclosed a kind of i.e. processing scheme of " PNA ' S " concentration of hydrocracking process polynuclear aromatic compound that is used for reducing, promptly separate the hydrocracking effluent in the fractionator, the fractionator oil foot is contacted with the sorbent material that optionally is detained the PNA compound in adsorption unit, again the circulation of fractionator oil foot is turned back in the hydrocarbon hydrocracking reaction device.
Licensed to people's such as Rahbe US4 on April 7th, 1989,655,903, introduced a kind of method that improves the resistates grade, promptly by the way of resistates and a kind of light hydrocarbons solvent being removed the unstable multinuclear hydro carbons that is known as coke precursors, and from unconverted resistates, isolate the multinuclear hydro carbons.
According to the present invention, provide a kind of and from hydro carbons treated oil stream, removed the method for stablizing polycyclic aromatic dimer, this method may further comprise the steps:
(a) hydrocarbon ils stream is sent into the hydrocarbon hydrocracking reaction device to produce lightweight oil stream and heavy effluent oil stream;
(b) make to small part heavy effluent oil stream and contact, contain with production and stablize the sedimentary mixing oil of polycyclic aromatic dimer and flow with lightweight paraffin oil stream; With
(c) in the operation of hydrocracking device, separation and discharge contain the precipitation of polycyclic aromatic dimer from mixing oil stream.
Key of the present invention is have a kind of in this system or several polycyclic aromatic dimers existence, and manage to make its precipitation.In other factors, the present invention is based on our discovery, and the scale-forming compound that promptly is present in the problematic hydro carbons refining oil stream mainly is two coronene, coronene ovalene, two ovalenes or their mixture.Compare with relative unstable polynuclear aromatic family's material promptly unstable " PNA ' S ", they are stable compounds.Measure through us, main dimerization reaction as shown in Figure 1.Before this is found, it is believed that foulant is the low-molecular weight compound of coronene and benzo coronene and so on.Be familiar with scale-forming compound and just can have controlled its precipitation, and can from other valuable hydrocarbon-type oil stream, remove them in normal operation refining operating period.
Though the present invention can be used for any refining oil stream of stablizing polycyclic aromatic dimer that contains, but, we find that the present invention is specially adapted to handle hydrocarbon hydrocracking reaction device effluent, be particularly useful for the effluent when the hydrocracking raw material is vacuum gas oil, produced, be applicable to that more processing works as vacuum gas oil and contact with catalyzer, as entering before the hydrocarbon hydrocracking reaction device effluent that is produced when Residual oil desulfurization (RDS).The present invention also is specially adapted to hydrocracking raw material such as Residual oil deutero-vacuum gas oil, coker gas oil and FCC turning oil, particularly infeeds Residual oil deutero-turning oil by FCC apparatus.
Although do not do such qualification, we find that the inventive method is well suited for processing from the effluent in the fixed-bed reactor.
For the Ppolynuclear aromatic dimerization foulant of control stabilization is precipitated out from the hydrocarbon hydrocracking reaction effluent, we find to add lightweight paraffin oil stream is very useful.And the amount of the paraffin that discovery is added and the resultant temperature of temperature and mixed flow are very important.
Another kind of implementation method of the present invention is to add flocculation agent so that control scale-forming compound precipitation, the end capped polystyrene of vinyl acetate copolymer and carboxylicesters is preferred flocculation agent, with respect to sedimentary Ppolynuclear aromatic dimeric compounds foulant from mixing oil stream, the mass ratio of its adding is 100: 1～20: 1.
In case in mixing oil stream, realize precipitation control, just must be before not containing the dirty processing units of mixing oil stream contact of foulant, separation and remove sedimentary foulant-stablize Ppolynuclear aromatic dimeric compounds from mixing oil stream.In the preferred embodiment of the invention, realize separating by filtering, but sedimentation or employing centrifuging are as also can with settling centrifuge.
With the concentration that only is suspect to be pollutent with minimizing be purpose need be from the hydrocracking recirculation loop system discharge or the existing currently known methods of " removing " material different, important aspect of the present invention is to have only the valuable hydrocarbon hydrocracking reaction effluent of a very little part to be removed.Another importance of the present invention is that it has the polycyclic aromatic dimer foulant itself to work, and it is inoperative to dipolymer precursor such as coronene or ovalene, so just, make the lightweight aromatic essence be cracked into byproduct, avoid too much running off low value oil stream as oil fuel, it is retained in the more valuable oil stream so that might reform and mix.
Fig. 1 represents to generate the chemical reaction of the stable Ppolynuclear aromatic dimeric compounds of fouling.
Fig. 2 is the process flow sheet of the explanation preferred embodiment of the invention.
Used herein term " hydrocracking " is meant with hydrogen hydrocarbon-type oil stream changed into the working method of hydrocarbon products as petroleum fractions, and the concrete raw material of sending into the hydrocarbon hydrocracking reaction device comprises that gas oil, heavy oil, fractionation cross the fuel oil residuum and the vacuum of gasoline and kerosene and distillate Residual oil.The hydrocarbon hydrocracking reaction effluent is liquid and gas two-phase mixture normally, and wherein the main component of liquid phase effluent is C
5(comprise C
5) above hydro carbons.
Term used herein " polycyclic aromatic dimer " i.e. " PAD " is meant the compound of stable dimerization, and it can not react or dimerization again, and this is owing to ring in the molecule is added to the exercising result that forms molecule Scholl condensation on the naphthalene.The example of dimeric compounds is two coronene, coronene ovalene, two ovalenes, and they by coronene, ovalene or the two the Scholl condensation take place and produce.
Term used herein " flocculation agent " is meant the oil soluble organic compound, can separately or mix to add to bring out or to promote the precipitation of insoluble compound in the hydrocarbon-type oil stream.
Term used herein " paraffin oil stream " is meant and contains a large amount of stable hydrocarbon, is preferably straight chain or just-liquid flow of paraffin stable hydrocarbon, and suitable paraffin oil stream comprises lightweight straight-run spirit, in advance through the refining oil stream of a step or the operation of multistep machining cell, or C
3～C
5Hydrocarbon material stream.In addition, can be with the refining process of paraffin stream adding from external source.
Referring to Fig. 2, through managing 1 raw material to be sent into, this raw material can be the hydrocarbon raw material that is particularly useful as hydrocracking.Preferred raw material is that boiling point is about 500～1100 vacuum gas oil and boiling point and is about 400～1000 gas oil, and effect is good especially when method of the present invention is used for boiling point and is about the hydrocracking raw material of 650～1100 ℃ of vacuum gas oils.
Through managing 20 clean circulating hydrogen or hydrogen make-up sent in the complete processing, be compressed to operating pressure at it and be about 750～10,000, especially when 1000～4000 pounds/square inch (psig), be admitted to the first step hydroconversion zone 5 of secondary hydrocracker with hydrocarbon raw material.Should notice that Fig. 2 is the process flow sheet of simplifying, and for clarity sake has several processing unitss such as separator, well heater and compressor to be omitted.The pressure of first step hydrocarbon hydrocracking reaction device 5 and temperature change according to the degree of raw materials used in the technology, the catalyst type and the hydrocracking that requires, and make this complete processing have severity with these reaction conditionss.The effluent of first step hydroconversion reactions device leaves first step hydroconversion zone 5 through managing 6, through manage 12 enter fractionation plant 40 or other dirty purification apparatus before, send the hydrogen sulfide stripping zone 14 in the one embodiment of the invention to.
In preferred embodiment shown in Figure 2, before our discovery, dirt progressively accumulative side effect is the most general in by oil stream pipe 42,43 and 45 " recirculation loop " (see figure 2)s of forming.For the speed that dirt in the control recirculation loop gathers, shown in Fig. 2 oil stream pipe 41, must discharge or " removing " a large amount of valuable recycle substance in the past.This method of removing generally will be got rid of a part of oil fuel or deliver to coker.
In technology of the present invention, we find that the effluent of controlling from second stage hydrocracking district 48 45 is effective especially to remove the part polycyclic aromatic dimer, and polycyclic aromatic dimer is that some are easy to the scale-forming compound that loses liquor and stop up dirty refining equipment.Adopt filtration or other physical separation method such as centrifugation or settling process can realize optionally removing and stablize the polycyclic aromatic dimer foulant.But at first need from the refining liquid oils stream that contains scale-forming compound, it optionally to be precipitated out.
When forming mixing oil stream, we have obtained the unexpected effect that thing falls in selective precipitation foulant Ppolynuclear aromatic two in a certain amount of paraffin oil stream being joined the oil stream that contains PAD ' S.Paraffin oil flows and contains PAD oil stream with 1: 10～1: 2, be preferably 1: 3～and mol ratio was mixed in 1: 5.Because solvability and the solvability in paraffin oil stream as hydrogen sulfide stripping reflux (as Fig. 2 pipe 10 shown in) of PAD ' S in the oily stream of effluent (as managing shown in 43) of second stage hydrocracker 48 has very big-difference, so realize precipitating by these two oily streams are combined.According to the preferred embodiment of the invention, paraffin oil stream 10 is mixed to form mixing oil stream 13 with the hydrocarbon-type oil stream 11 of the stable Ppolynuclear aromatic dimeric compounds that contains the energy fouling.In a preferred embodiment, paraffin oil stream is H
2The S stripper plant refluxes.Also can adopt other kind lightweight oil stream as the condensate fractionation thing.
At least after containing the PAD ' S of partly precipitated therein, oil stream 13 enters the disengaging zone, under the condition of not interrupting the operation of hydrocracking device, at this sedimentary PAD foulant of at least a portion is removed from technology.Be preferably mixing oil stream 13 and at first enter " knockout drum " formula separator 24, send into setting tank 28 by the liquid phase oil stream 26 that wherein comes out, in this preferred embodiment, setting tank 28 has about 6 hours residence time, before setting tank 28, can adopt radiator cooler such as air-cooler 27 further to help to control the precipitation that foulant is stablized polycyclic aromatic dimer.Transfer lime 29 is filtration unit 30 feed, preferably is designed to the dual system of continuous filtration operation.To stablize polycyclic aromatic dimer precipitation and from the hydrocracking system, discharge or remove and deliver to storage or processing through managing 22.Return oil stream by oil stream 32 expressions that filtration unit 30 comes out, owing to removing of PAD in the disengaging zone, it has lower PAD concentration than the oil stream 11 or the second stage hydrocracking effluent 43 that extracted.It should be noted that the preferred embodiment of the invention is illustrated in figure 2 as the secondary hydrocracking process, but is not limited to this.In the disengaging zone, by mass, have only relative small portion mixing oil stream 13 from technology, to be removed with the sedimentary form of PAD.By adopting technology of the present invention, as manage 41 represented very general excessive discharge hydrocarbon liquids or " removing " before the present invention and be reduced or eliminated.
Filtered oil stream 32 is transported to down flow device, perhaps in a preferred embodiment, before hydrogen sulfide stripper plant 14 its effluent with second stage hydrocracking device is mixed.Because the PAD that q.s arranged 20 is removed in the disengaging zone, making the liquid hydrocarbon material that exists in Fig. 2 embodiment technology can not damage dirty refining equipment is one of main purpose of the present invention.
In another preferred embodiment of the present invention, mixing oil stream 13 also contains by flocculation agent fragment position 23 and joins flocculation agent in the oil stream 10.Compare with the content of PAD, by weight, the flocculation dosage of adding is 100: 1～20: 1.When flocculant addition is 40: 1～50: 1, can obtain good especially result.We find owing to there is the end capped polystyrene of such flocculation agent such as ethylene vinyl acetate copolymer or dicarboxylic ester to exist, and fouling PAD precipitation is strengthened or quicken.The adding flocculation agent can reduce the add-on of olefin material, can obtain enough PAD precipitations from mixing oil stream.The flocculation agent that we find is not only to have had the good aliphatics characteristic that is soluble in the hydrocracking effluent but also have and the strong polar compound molecule of PAD ' S effect.The other parts of molecule should have chemical energy group very strong and two coronene or other PAD molecularity or group.This can adopt polar group to realize, also can adopt PAD molecule De 兀 electronics had than the group of strong affinity and realize.There is the polymkeric substance that the compound of good several types especially contains long hydrocarbon chain and polar functionality can satisfy this requirement.With contain before PAD oil stream mixes, at first should make the flocculation agent dilution by mixing with the lightweight olefin material, flow requirement with minimizing lightweight paraffin oil.So just guaranteeing has good dispersiveness, causes two coronene of major part and other PAD molecule to be removed.
Since contain in the pipe 11 of PAD from the effluent of second stage hydrocracking device and with it between the phase blended paraffin oil stream 10 the general temperature difference be about 300 °F, to be lower than with oil before paraffin oil stream mixes and flow temperature so the mixing oil that generates flows 13 temperature.We find that temperature descends about 25～100 °F and can obtain very ideal and strengthen the sedimentary effect of PAD, and can too much not reduce the thermo-efficiency of hydrocracking refining process and total efficient.Perhaps by the control mixing velocity or by adopting known outer refrigerating unit heat exchanger, further the cooling mixture temperature is so that the PAD precipitation reaches optimization.Additional refrigerative degree depends on refining design and total refining thermal equilibrium, so this is relevant with concrete refining.
In another preferred embodiment of the present invention, we find that by mass, through the PAD content of mensuration in the mixing oil stream part of disengaging zone, the ratio that adds flocculation agent is that 40: 1～50: 1 effects are good especially relatively.
According to the speed of removing, when refining on a large scale in the separation column oil foot 41 the general concentration of two coronene be 30～70ppb.The concentration of two coronene is 50～200ppb in the reactor effluent oil stream 11.
The embodiment that below relates to all respects of the present invention is in order to being illustrated the present invention, but to the present invention without any restriction.
The determination and analysis of embodiment 1 PAD dirt
During shut-down operation, from hydrocracker, obtain the oil-containing settling.This sample was preserved for two weeks, adopt the exhaustive extraction method then, handle, obtain deposition residues with dihydro methane solvent and Soxhlet's extractor.
With PAD ' S content in the beam split fluorometry test samples.Perkin-Elmer MEP-66 type beam split fluorescence analyser measurement with synchronous scanning has trace P AD ' S mixture, does not need it is separated.The maximum wavelength of these PAD ' S excites to be penetrated maximum with minimum wavelength and differs about 5～20nm.When with predetermined δ-wavelength value to the beam split fluorescence analyser excite and when launching monochromator and carrying out synchronous scanning, every kind of PAD has the monochromatic light bands of a spectrum to produce.In this way, can't see other excitation band, also can't see emission band away from δ-value outside the maximum excitation band away from the δ-value beyond the minimum emission wavelength ranges.
The hydrocracking deposition residues of being detained with the mass spectrometry analysis (carrying out after the limit extraction with methylene dichloride) shows that it is 596 and 694 homologue that two kinds of initial mass are arranged.It is believed that this is the fusion product of two coronene molecules or a coronene and an ovalene molecule, generate the PAD ' S that is named as two coronene and coronene ovalene respectively.These structure formations have obtained assert because other issuable isomer will be according to the order of sequence on a ring in conjunction with and obtain, and people do not see any other intermediate PAD ' S, therefore, it is impossible carrying out coupled in series on a ring.
Preparation is dissolved in 1,2, and the saturated deposition residues solution of 4-trichloro-benzene (TCB) adopts field desorption(FD) mass spectrometry and beam split fluorometry to detect, and detects the spectral response curve of hydrocracking resistates and pure two coronene.Relatively both excitation spectrums show and almost are identical configuration, and just because the alkyl metalepsy, the spectrum configuration of resistates is shifted to big wavelength a little.
For synchronous scanning fluorescent method (SSF), adopt 6nm δ-value, be that the band of pure two coronene solution is poor because find this value.This δ-value requires monochromator must have the seam of 2nm wide.For direct analysis usefulness, saturated solution concentration is too big, so want preparation standard solution, in order to obtain the enough solution of dilution, with 345 milligrams of microbalance weighings, is dissolved among the 500ml TCB, then with this solution dilution to 1 of 5ml: 100.
The synchronous scanning of this solution shows two main peaks: first main peak center is positioned at 510nm, is that the second main peak center is positioned at 545nm by due to two coronene, it is believed that it is by due to the coronene ovalene.(ratio at two peaks approximately detects the ratio that this material total concn is seen with mass spectroscopy exactly.) denseer sample demonstrates another peak at the 610nm place, be likely due to " two ovalenes " that forms by the condensation of two ovalene molecules.
The repeat sample of hydrocracking raw material and hydrocracking turning oil is through synchronous scanning, and in the spectral range of two coronene characteristics, former material samples does not demonstrate tangible peak, but turning oil has then demonstrated.The used concentration that is dissolved in sample among the TCB, raw material sample are 1.0g/10ml, and the circulation oil sample is 0.1g/10ml.When with turning oil peak and the comparison of settling " standard " peak, two coronene concentration are 70ppb in first kind of sample, and this concentration is 85ppb in second kind of sample.
Carry out two tests, measure by adding the promptly anti-solvent of poor solvent (using paraffin solvent at this) is removed two coronene from solution amount.First test is to prepare saturated sample in order to confirm the mechanism of this discovery, to comprise by add some solid two coronene powder (being made by the purification of hydrocracking settling) in hydrocracking turning oil.On hot-plate, the 200ml sample aliquot is heated to about 400 °F, add different quantities 1: 1 just-pentane and 2-methylbutane mixture, place this solution 1 hour (in 400 °F), take out oil sample then, analyze two coronene with synchronous scanning fluorescent method (SSF), because adding the diluting effect that causes, pentane admixture calculates the amount of two coronene that are removed by determining measured amount and considering.
The amount of amount of pentane solution (volume ratio) and two coronene that stay is as shown in table 1 below:
Table 1
Two coronene solvabilities
(1)(ppb)
Volume ratio (oil: pentane)
Temperature (°F) net weight
(2)5: 13: 12: 1
200 65 10 7 7
250 90 20 16 13
300 155 35 24 22
350 215 60 52 44
400 280 90 79 68
(1) 1: 1 just-pentane and 2-methylbutane mixture be as anti-solvent.
(2) be dissolved in the amount of two coronene in the saturated solution.
Table 2
The amount of removing of two coronene
400 °F
Experiment sequence number saturated turning oil pentane admixture remove two
Volume, ml volume, ml coronene, %
1 200 50 70
2 200 100 76
3 200 200 87
4 200 400 99
Second method also comprises one at the original place filtration step, and filtration unit is the metal tin that volume is about 500ml.And it has chuck so that be heated.Filtering table is equipped with 10 micron filters in the bottom.Can adopt at the nitrogen tube inlet at top and exert pressure.Pressure boost is then analyzed with the SSF method so that displace sample, when further determining the solvability scope of two coronene, in the oily sample that contains two coronene, add different volumes just-pentane/2-methylbutane mixture.Every operation all carries out under 400 °F.The effect of removing of two coronene is listed table 2 in.
Under 200～400 temperature, measure the solvability of two coronene by make three kinds of saturated methods of different refining oil stream samples with two coronene.Owing to be difficult to filter these oil samples under comparatively high temps, we are sedimentation oil sample simply only, solid two coronene at the bottom of removing bottle.Then, we detect two coronene that are dissolved in the edible vegetable oil sample of upper strata with the beam split fluorometry.
Three kinds of refining oil streams, i.e. thermal low-pressure separators (HLPS) oil foot, H
2The solvating ability of S stripping oil foot and separation column oil foot (circulation fluid) has a great difference.We find that two coronene are at H
2Solubleness in the S stripping oil foot almost exceeds 10 times than its solubleness in the HLPS oil foot.The key distinction of two kinds of oil streams is to have light hydrocarbons to exist in the HLPS oil foot.This class hydrocarbon matter hydro carbons (mainly being the paraffin composition) is with the H in the stripper
2S is separated together to be fallen.This class olefin material can reduce the solvating ability of stripping oil foot to PAD ' S greatly.
Embodiment 4 flocculation agents
Whether help to remove PAD ' S in order to get chemical floc clear, we have carried out some shaker tests.In these tests, in that the secondary circulation oil sample (separation column oil foot) after saturated is that oil-soluble polymers is handled with small amount of flocculant by two coronene under 100 °F, the polymkeric substance of test usefulness comprises: polyvinyl acetate, ethylene vinyl acetate copolymer, poly-(2-ethene) pyridine/styrol copolymer and the terminal polystyrene of dihydrate, need not cool off these samples, impel dissolved PAD ' S precipitation with 100ppm dosage polymkeric substance, and flocculate big and the visible diameter has several millimeters cotton-wool thing.In these trials, we can be with the concentration of two coronene from about 2, and 000ppb is reduced to about 20ppb, in addition, the coronene throw out of 50-80% is arranged in the sample.Although some polymkeric substance can produce bigger heavier cotton-wool thing than other polymkeric substance, they all are being effective aspect the throwing out that improves PAD ' S.
List table 3 by the about 2000ppb of original sample concentration in to the two coronene concentration results that produced:
Table 3
Flocculation agent is analyzed
(1)
Polyvinyl acetate 130ppb
Ethene/PVA copolymer 1 25ppb
Poly-(2-ethene) pyridine/styrol copolymer
(2)245ppb
The end capped polystyrene 20ppb of dicarboxylic ester
Poly-(butyl methacrylate/methacrylic acid
Isobutyl ester) copolymer 1 80ppb
Polyvinyl methyl ethermaleic anhydride 235ppb
Poly-(2-ethene) pyridine 250ppb
(1) former two coronene concentration are 2000ppb.
(2) the cotton-wool thing is very thin suspended substance.
Under the very low situation of concentration, bringing out precipitation with chemical method can be so ineffective.
This test shows, it is the same to bring out precipitation with Re Fa or chemical method, and filtration can reduce the PAD ' S concentration in the HLPS oil foot.
For this test, we have used very a spot of refining HLPS oil foot sample, 415 °F down with two coronene with this hold-up, deep fat was kept under nitrogen blanket about 24 hours, to set up the balance between dissolved two coronene and its solid piece.During this period, clearly because oxygenizement causes oil blackening a little.The poorest oil in 415 saturated this oil is considered to from HLPS down.The concentration of PAD ' S is approximately 120ppm in oil.
Then, filter the saturated oil sample of this two coronene of 4～50ml with small-sized intermittent type pressure filter, with heating zone parcel strainer fuselage, temperature is remained in the several years of our regulation with temperature regulator, filtration medium is that 10 microns 47 mm dia tetrafluoroethylene (teflon) filtering membranes are formed by average pore size, on filtering membrane, places a glass fibre first pre-filter, so that the blocked possibility of the more filtration environment of real simulation fabric tube strainer, and minimizing membrane filtration spare.
Used flocculation agent is the terminal polystyrene of dihydrate that is dissolved in advance in the high boiling range light cycle in these two tests, below is the explanation to four samples:
1. this sample is cooled to 275 °F by 415 °F in about 5 minutes, and after filtration, does not add flocculation agent.
2. in sample, add the 100ppm flocculation agent, in about 5 minutes, it is cooled to 275 °F by 415 °F, and filters it.
3. in about 5 minutes, sample is cooled to 275 °F by 415 °F, kept 25 minutes down and filter it in 275 °F, do not add flocculation agent.
4. still in sample, add the 100ppm flocculation agent, it is cooled to 275 °F by 415 °F, keep 25 minute down, and filter it in 275 °F.
Under 275 °F, with having only 2～3 pounds/inch
2Individual pressure reduction all filters all samples being no more than in 1 minute.Adopt so fast and filter, we do not need to use in test the glass fibre first pre-filter certainly.
The beam split fluorometric analysis of filtrate shows two following coronene concentration:
1.25ppb。
2.20ppb。
3.25ppb。
4.35,45ppb(detects twice).
We do not understand the result of sample 4, might be the filtration elements of some bypass or owing to have the hole or tear on the membrane filtration spare, or since film be not placed in suitably due to its seat surface.(4 result approaches formerly to measure 275 two coronene about 45ppm of the numerical value of solubleness in HLPS down.）
As if this result shows, the test 3 and 4 extra amounts that can not increase the PAD ' s that removes in 25 minutes of being detained.But should be noted that 415 following heated oil blackening to influence the dissolving power of HLPS liquid or the ability of polymer precipitation PAD ' s.
These tests show, adopt cooling and filter half that the concentration of two coronene in HLPS liquid can be reduced to its original content value, adopt cooling and with flocculation agent perhaps reduce also some more.
Be applied to the method for refining process
To be that 650～1100 vacuum gas oil is sent into hydrocarbon hydrocracking reaction device (hydrocracker) from Residual oil desulfurizer mid-boiling point.Heavy effluent in the hydrocracker is sent into H
2The S stripper plant at this, contains C
5And C
5Above whiteruss overhead product is being back to H
2Condensation in overhead condenser before the S stripper plant.The 500BPD pentane admixture is mixed with 1000 barrels of/day heavy effluents (415) that contain polycyclic aromatic dimer from second stage hydrocracker.Mixing oil stream is sent in 325 °F and 180 pounds/inch
2(gauge pressure) be the knockout drum of operation down, and it is in 6 hours the setting tank that the liquid phase of being come out by this knockout drum flows into the residence time, and the fluid inflow filter that comes out in the setting tank is at this, with two online filtering-depositings of filtering system.Stablize gathering and precipitating of polycyclic aromatic dimer for bringing out, add flocculation agent at the knockout drum upper reaches.Fin fan-type air-cooler is installed to help cooling between knockout drum and setting tank, and is promoted more precipitation.According to the dimer content operating cooler of learning by spectrochemical analysis.Discharge be will precipitate at the filtration unit place and storage or processing place delivered to.Clear liquid in the device of inherent filtration in the future turns back to heavy effluent oil stream, therefrom obtains 1000BPD415 compound.
For the formation of foulant in the minimizing system, present embodiment has been removed to move from heavy effluent oil stream and has been decided polycyclic aromatic dimer, has so just eliminated the requirement of removing 2000BPD oil stream from the separation column oil foot.Therefore, the material of a large amount of hydrocrackings finally is transformed into valuable jet engine oil, diesel oil and other products in separation column, and the product gross profits is increased.
The economic benefit of present embodiment is summarised in the following table, can realize net profit ＄ every day more than 60,000, and above-mentioned said separation and filter plant investment are ＄ 750,000.(table 4 is seen the literary composition back)
To present technique field ordinary skill, according to above description and accompanying drawing, utilize discovery of the present invention to improve and change is conspicuous, belong to these claims institute restricted portion.
Table 4
The hydrocracking economic benefit of maximum jet-propelled engine oil output
(1)
Remove radix
(2)Be added with the situation of flocculation agent
(3)
The product index
$/B MBPOD M$/D MBPOD M$/D
Petroleum naphtha 28.00 13.2 369.6 13.2 369.6
Jetting type engine oil 33.00 28.9 953.7 30.9 1019.7
H
2Loss
(4)4.00 2.0 6.8-0.0
Total income 1330.1 1389.3
Incr.Op. price M$/OD
Flocculation agent
(5)-0.2
The PCA scavenging agent
(6)3.6-
Income-Op price 1326.5 1389.1
Amount to
Day profit M$/every day-62.6
Investment M$-750.0
Time of payment (fate)-12.0
(1) overhead product hydrocracking device among the 40MBPOD.
(2) 2MBPOD of control PCA formation removes.
(3) filtration of 5MBPOD does not increase manpower or utilizes cost.
(4) because of the 850SCF/H of oil fuel composition hydrogenation, ＄ 4/1000SCFH
2
(5) 100ppm flocculation agent, 1.25/ pound of ＄ does not add cooling.
(6) because hydrocracker is cleared up PAD sedimental shutdown period (increasing by 3 days shutdown period)
Claims (24)
1, a kind ofly from the hydrocracking effluent of hydrocarbon raw material, removes the method for stablizing polycyclic aromatic dimer, comprise
(a) in the hydrocracking device, send into hydrocarbon raw material to produce lightweight effluent oil stream and heavy effluent oil stream;
(b) near small part heavy effluent oil stream flows with mol ratio 2: 1-10 with the lightweight paraffin oil: 1 contacts, and contains the sedimentary mixing oil stream of polycyclic aromatic dimer with generation; The temperature of the lightweight paraffin oil stream before the contact should be enough low, reducing the temperature of mixed flow, thereby promotes the precipitation of the fragrant dipolymers of many cyclophanes; With
(c) simultaneously, from mixing oil stream, remove and be separated to small part and contain the precipitation of stablizing polycyclic aromatic dimer in the operation of hydrocracking device.
2, method according to claim 1, wherein hydrocarbon raw material is a vacuum gas oil.
3, method according to claim 1, wherein hydrocarbon raw material contacted with desulfurization catalyst before entering the hydrocarbon hydrocracking reaction device.
4, method according to claim 1, wherein separating step comprises filtration.
5, method according to claim 1, wherein the hydrocarbon hydrocracking reaction device is fixed-bed reactor.
6, method according to claim 1, wherein lightweight paraffin oil stream is from H
2The overhead product oil stream of S stripper plant.
7, method according to claim 5, wherein the contact in (b) step is carried out in the second stage oil foot effluent turning oil stream from two-stage hydrocarbon hydrocracking reaction device.
8, method according to claim 1 wherein before contact procedure, is carried out subcooling with paraffin oil stream.
9, method according to claim 1, wherein polycyclic aromatic dimer is selected from one group of material of being made up of two coronene, coronene ovalene, two ovalenes or its mixture.
10, method according to claim 1 wherein added flocculation agent in the mixed flow that step (b) produces before step (c) precipitation separation.
11, according to the method for claim 10, wherein flocculation agent is selected from vinyl acetate copolymer, the terminal polystyrene of dihydrate and polyvinyl acetate.
12, according to the method for claim 10, wherein flocculation agent at first mixes with a certain amount of lightweight paraffin oil stream so that make reagent be dissolved in heavy effluent oil stream.
13, according to the process of claim 1 wherein that flocculation agent is mixing with flowing with the lightweight paraffin oil before heavy effluent oil stream contact.
14, according to the process of claim 1 wherein before from mixing oil stream, isolating precipitation, flocculation agent is added in the mixing oil stream.
15, according to the process of claim 1 wherein that separating step comprises filtration.
16, according to the process of claim 1 wherein that separating step comprises centrifugation.
17, according to the process of claim 1 wherein that separating step comprises sedimentation mixing oil stream.
18, basis the process of claim 1 wherein that separation is to realize on the surface that polycyclic aromatic dimer is gathered by precipitation is deposited to, and regularly removes precipitation simultaneously in the operation of hydrocracking device.
19, according to the method for claim 10, wherein be present in mixing oil stream in detected PAD amount compare, the add-on of flocculation agent is 100: 1-20: 1.
20, according to the process of claim 1 wherein that hydrocarbon raw material effluent oil stream is vacuum gas oil.
21, according to the process of claim 1 wherein that lightweight paraffin oil stream is the processing condensation product from separation column.
22, according to the process of claim 1 wherein lightweight paraffin oil stream be cooled before heavy effluent oil stream mixes.
23, contact and the heavy effluent oil of separating step is a part from partial total oil foot effluent oil stream of two-stage hydrocracking device according to the process of claim 1 wherein.
24, according to the process of claim 1 wherein that heavy effluent oil stream is selected from coker gas oil, heavy recycle stock and intermediate turning oil.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/567,427 US5232577A (en) | 1990-08-14 | 1990-08-14 | Hydrocracking process with polycyclic aromatic dimer removal |
| US567427 | 1990-08-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1059928A CN1059928A (en) | 1992-04-01 |
| CN1027176C true CN1027176C (en) | 1994-12-28 |
Family
ID=24267109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN91108862A Expired - Fee Related CN1027176C (en) | 1990-08-14 | 1991-08-14 | Hydrocracking process with polycyclic aromatic dimer removal |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5232577A (en) |
| EP (1) | EP0543933A4 (en) |
| JP (1) | JPH06500354A (en) |
| KR (1) | KR930702473A (en) |
| CN (1) | CN1027176C (en) |
| WO (1) | WO1992003520A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5605606A (en) * | 1993-07-19 | 1997-02-25 | Nalco/Exxon Energy Chemicals. L.P. | Removal foulants from distillation train using non-solvent precipitation |
| JP4076749B2 (en) * | 2001-10-15 | 2008-04-16 | 富士フイルム株式会社 | Conductive organic compound and electronic device |
| FR2883004B1 (en) | 2005-03-09 | 2007-04-20 | Inst Francais Du Petrole | HYDROCRACKING PROCESS WITH RECYCLING COMPRISING THE ADSORPTION OF POLYAROMATIC COMPOUNDS OF THE RECYCLED FRACTION ON A MACROPORTED CONTROLLED CONTENT SILICA-ALUMINUM ADSORBENT |
| FR2883005B1 (en) | 2005-03-09 | 2007-04-20 | Inst Francais Du Petrole | HYDROCRACKING PROCESS WITH RECYCLING COMPRISING THE ADSORPTION OF POLYAROMATIC COMPOUNDS OF MACROPORATED LIMITED-SILAGE ALUMINA-ADSORBENT RECYCLED FRACTION |
| US7674369B2 (en) | 2006-12-29 | 2010-03-09 | Chevron U.S.A. Inc. | Process for recovering ultrafine solids from a hydrocarbon liquid |
| US7658895B2 (en) | 2007-11-28 | 2010-02-09 | Chevron U.S.A. Inc | Process for recovering base metals from spent hydroprocessing catalyst |
| US8221710B2 (en) | 2007-11-28 | 2012-07-17 | Sherritt International Corporation | Recovering metals from complex metal sulfides |
| CN101918132A (en) | 2007-11-28 | 2010-12-15 | 雪佛龙美国公司 | Process for recovering base metals from used hydroprocessing catalyst |
| AU2010229809B2 (en) | 2009-03-25 | 2015-02-12 | Chevron U.S.A. Inc. | Process for recovering metals from coal liquefaction residue containing spent catalysts |
| CN105073956B (en) | 2013-03-15 | 2017-10-20 | 鲁姆斯科技公司 | Hydrotreating hot cracked product |
| US20140323788A1 (en) * | 2013-04-24 | 2014-10-30 | Uop, Llc | Process for modifying an apparatus and for removing one or more contaminants |
| FR3091535B1 (en) * | 2019-01-09 | 2021-01-08 | Ifp Energies Now | TWO-STAGE HYDROCRACKING PROCESS INCLUDING A HYDROGENATION STAGE DOWNSTREAM OF THE SECOND HYDROCRACKING STAGE FOR THE PRODUCTION OF MEDIUM DISTILLATES |
| US11066610B2 (en) | 2019-05-28 | 2021-07-20 | Saudi Arabian Oil Company | Systems and processes for suppressing heavy polynuclear aromatic deposition in a hydrocracking process |
| US11180701B2 (en) | 2019-08-02 | 2021-11-23 | Saudi Arabian Oil Company | Hydrocracking process and system including separation of heavy poly nuclear aromatics from recycle by extraction |
Family Cites Families (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3546098A (en) * | 1968-07-24 | 1970-12-08 | Chevron Res | Making a lube oil by hydrocracking and solvent extraction |
| US3579437A (en) * | 1969-04-03 | 1971-05-18 | Sun Oil Co | Preparation of high v.i. lube oils |
| US3562145A (en) * | 1969-08-15 | 1971-02-09 | Mobil Oil Corp | Stable hydrocarbon lubricating oils and process for forming same |
| US3660273A (en) * | 1969-11-12 | 1972-05-02 | Texaco Inc | Production of improved lubricating oils by hydrocracking and solvent extraction |
| US3619407A (en) * | 1969-12-17 | 1971-11-09 | Union Oil Co | Hydrocracking process with benzcoronenes bleedstream |
| US3766055A (en) * | 1971-07-19 | 1973-10-16 | Texaco Inc | Lubricating oils by hydrocracking and solvent extraction |
| US3925220A (en) * | 1972-08-15 | 1975-12-09 | Sun Oil Co Pennsylvania | Process of comprising solvent extraction of a blended oil |
| US3929617A (en) * | 1972-08-31 | 1975-12-30 | Exxon Research Engineering Co | Hydrocracking extraction process for lubes |
| US3781196A (en) * | 1972-09-01 | 1973-12-25 | Sun Oil Co Pennsylvania | Stabilizing a hydrocracked lube oil by solvent extraction |
| US3790470A (en) * | 1972-12-06 | 1974-02-05 | Texaco Inc | Production of lubricating oils |
| US3882013A (en) * | 1973-03-15 | 1975-05-06 | Yakov Rafailovic Katsobashvili | Method of producing highly aromatized low-sulphur hydrocarbon petroleum stock |
| US3923636A (en) * | 1974-06-03 | 1975-12-02 | Texaco Inc | Production of lubricating oils |
| US4235701A (en) * | 1979-03-30 | 1980-11-25 | Atlantic Richfield Company | Aromatics from dripolene |
| US4411768A (en) * | 1979-12-21 | 1983-10-25 | The Lummus Company | Hydrogenation of high boiling hydrocarbons |
| US4447315A (en) * | 1983-04-22 | 1984-05-08 | Uop Inc. | Hydrocracking process |
| US4655903A (en) * | 1985-05-20 | 1987-04-07 | Intevep, S.A. | Recycle of unconverted hydrocracked residual to hydrocracker after removal of unstable polynuclear hydrocarbons |
| US4676886A (en) * | 1985-05-20 | 1987-06-30 | Intevep, S.A. | Process for producing anode grade coke employing heavy crudes characterized by high metal and sulfur levels |
| US4698146A (en) * | 1986-01-23 | 1987-10-06 | Uop Inc. | Hydrocracking and recovering polynuclear aromatic compounds in slop wax stream |
| US4853104A (en) * | 1988-04-20 | 1989-08-01 | Mobil Oil Corporation | Process for catalytic conversion of lube oil bas stocks |
| US5007998A (en) * | 1990-03-26 | 1991-04-16 | Uop | Process for refractory compound conversion in a hydrocracker recycle liquid |
-
1990
- 1990-08-14 US US07/567,427 patent/US5232577A/en not_active Expired - Fee Related
-
1991
- 1991-08-05 JP JP3515617A patent/JPH06500354A/en active Pending
- 1991-08-05 EP EP19910916440 patent/EP0543933A4/en not_active Withdrawn
- 1991-08-05 WO PCT/US1991/005534 patent/WO1992003520A1/en not_active Application Discontinuation
- 1991-08-05 KR KR1019930700425A patent/KR930702473A/en not_active Application Discontinuation
- 1991-08-14 CN CN91108862A patent/CN1027176C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992003520A1 (en) | 1992-03-05 |
| EP0543933A1 (en) | 1993-06-02 |
| US5232577A (en) | 1993-08-03 |
| EP0543933A4 (en) | 1993-11-03 |
| KR930702473A (en) | 1993-09-09 |
| JPH06500354A (en) | 1994-01-13 |
| CN1059928A (en) | 1992-04-01 |
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